Vincent Gandon

Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182 Université Paris-sud

Sélectivité en catalyse moléculaire :

Assistance de la chimie théorique

IIIème Journée de Simulation Numérique en Chimie à Paris-S ud

12 novembre 2014

2

Thermal (Berthelot, 1866)

Catalytic (Reppe, 1948)

Catalytic (Vollhardt, 1970)

Metal-Catalyzed [2+2+2] Cycloaddition of Alkynes

Stoichiometric (Vollhardt, 1970)

CpCo(CO)

CoCp(CO)

CoCp

CpCo

CpCo

Co

CpCo

CpCo

CO

CO

Co

OC CO

Cp

3

Cobalt-Catalyzed [2+2+2] Cyclotrimerization of Alkynes

CpCo(CO)

CoCp(CO)

CoCp

CpCo

CpCo

Co

CpCo

CpCo

CO

CO

Co

OC CO

Cp

4

Cobalt-Catalyzed [2+2+2] Cyclotrimerization of Alkynes

Albright, T. A. J. Am. Chem. Soc. 1999, 121, 6055Koga, N. Bull. Chem. Soc. Jpn. 2005, 78, 781

5

B3LYP/6-311+G(2d,2p)

∆E (kcal/mol)

Metal-Assisted [4+2] Cycloaddition

J. Am. Chem. Soc. 2007, 129, 8860

PPh3 C2H4 THF

6J. Am. Chem. Soc. 2007, 129, 8860

Unassisted [4+2] Cycloaddition

PH3 PMe3 CO

0.0

Co

L

CpEE

CpCoL +

E

E

CpCo

L

+E E

CpCo

L

EE

(E = CO2H)

+18.0

29.8

29.2

90.8

B3LYP/6-311+G(2d,2p)

∆E (kcal/mol)

7Chem. Eur. J. 2007, 13, 7466

∆H298 (kcal/mol)

B3LYP/6-311+G(2d,2p)

Tethered Systems

8Chem. Eur. J. 2007, 13, 7466

∆H298 (kcal/mol)

B3LYP/6-311+G(2d,2p)

Tethered Systems

9Chem. Eur. J. 2007, 13, 7466

Tethered Systems

Cycloisomerization of enynes: Pt(II)

P

Pt(PhCN)2, (BF4)2

P

Ph Ph

Ph Ph 1

[Pt] (10 mol%)

CHCl3, rt, 20 h

[Pt] = PtCl2, 83%[Pt] = 1, 92%

2 3

MeO

MeO

MeO

MeO

B3LYP/LANL2DZ(Pt)/6-31G(d,p)

Cycloisomerization of enynes: Pt(II)

Cycloisomerization of enynes: Pt(II)

B3LYP/LANL2DZ(Pt)/6-31G(d,p)

Electrospray ionization tandem mass spectrometric experiments.Consecutive CAR/CID sequences (Collision-Activated Reaction, Collision-Induced Dissociation)

Mass spectroscopy (CAR/CID)

Cycloisomerization of enynes: Pt(II)

Mass spectroscopy (CAR/CID)

Cycloisomerization of enynes: Pt(II)

Cycloisomerization of enynes: Pt(II)

ChemCatChem 2009, 1, 138Chem. Sci. 2011, 2, 2417

16

Chatani, Org. Lett. 2006, 8, 2155

Cycloisomerization of enynes

17

Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527

B3LYP/LANL2DZ(Ga)/6-31G(d)

Cycloisomerization of enynes

18

Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527

B3LYP/LANL2DZ(Ga)/6-31G(d)

Cycloisomerization of enynes

∆G298 (kcal/mol)

V1

Diapositive 18

V1 le trans nonconj est écrit cis dans le papier !Vincent; 10/11/2014

19

Cycloisomerization of enynes

Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527

B3LYP/LANL2DZ(Ga)/6-31G(d)

GaCl2

H

H

GaCl2

H

H

H

G = 12.4 kcal/mol

G = 9.2 kcal/mol

+

H

GaCl2

+

∆G298 (kcal/mol)

20

B3LYP/LANL2DZ(Ga)/6-31G(d)

Cycloisomerization of enynes

Cationic Gallium(III) Complexes

Ga-F(1) 1.920(4) ÅSb-F(1) 1.987(1) ÅSb-F(2,3,4,5,6)av 1.87 Å

Inorg. Chem. 2013, 52, 11493Inorg. Chem. 2013, 52, 506Organometallics 2014, 33, 594

Cycloisomerization of enynes

Cycloisomerization of enynes

B3LYP/6-31G(d)

∆G298 (kcal/mol)

Cycloisomerization of enynes

25

B3LYP/6-31G(d)

Cycloisomerization of enynes

∆G298 (kcal/mol)

26

Cycloisomerization of enynes

B3LYP/6-31G(d)

∆G298 (kcal/mol)

Cycloisomerization of enynes

B3LYP/6-31G(d)

GaCl2L

H

H

LCl2Ga H

H

H

GaCl2L

H

G = ?

+

+

G = ?

E

E

E

E

E

E

(E = CO2Me)

E 7.5 kcal/mol

∆G298 (kcal/mol)

Bogdan Iorga (ICSN)Etienne Derat (P6)Tom Albright (Houston)Jeremy Harvey (Bristol)CRIHAN

Acknowledgements

Cycloisomerization of enynes: Pt(II)

B3LYP/LANL2DZ(Pt)/6-31G(d,p)

Cycloisomerization of enynes: Pt(II)

B3LYP/LANL2DZ(Pt)/6-31G(d,p)

Cycloisomerization of enynes

B3LYP/6-31G(d)

Cycloisomerization of enynes

B3LYP/6-31G(d)

Cycloisomerization of enynes

B3LYP/6-31G(d)